EP2374716A1 - Weiße Antistatikbeschichtung auf der Basis von hydroxyliertem Acryl - Google Patents

Weiße Antistatikbeschichtung auf der Basis von hydroxyliertem Acryl Download PDF

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Publication number
EP2374716A1
EP2374716A1 EP11305398A EP11305398A EP2374716A1 EP 2374716 A1 EP2374716 A1 EP 2374716A1 EP 11305398 A EP11305398 A EP 11305398A EP 11305398 A EP11305398 A EP 11305398A EP 2374716 A1 EP2374716 A1 EP 2374716A1
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EP
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Prior art keywords
composition
component
composition according
base
binder
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EP11305398A
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German (de)
French (fr)
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EP2374716B1 (en
Inventor
Stéphanie REMAURY
Pascale Nabarra
Olivier Guillaumon
Serge Reymond
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Centre National dEtudes Spatiales CNES
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Centre National dEtudes Spatiales CNES
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
    • B64G1/00—Cosmonautic vehicles
    • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
    • B64G1/226—Special coatings for spacecraft
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to electrically conductive coatings for the antistatic protection of dielectric or metal substrates, especially spacecraft, and in particular launchers and satellites. These coatings must meet several requirements: first of all, it is essential to avoid the accumulation of charge on the surface. Antistatic paints are therefore sought to avoid these so-called “flash over” phenomena (surface electrostatic discharges).
  • these coatings must participate in the thermal control of the machine. It is therefore important that the paint is white, to allow total reflection of solar radiation and avoid a heating of the machine that could result.
  • paints must meet very strict specifications in terms of solar absorption (alpha), infrared emissivity (epsilon), surface electrical resistance and adhesion.
  • a tin oxide pigment doped with antimony oxide and the paint containing it including the elimination of electrostatic charges. Nevertheless, said colored pigment must be mixed with a white pigment to meet the requirements of low solar absorption. Moreover, this pigment is expensive and no longer meets European environmental standards.
  • a paint based on tin oxide and antimony oxide is also described in FR 2,668,491 . Nevertheless, again, the addition of titanium dioxide is necessary to make the paint white.
  • US 3,538,022 discloses a method of manufacturing zinc oxide doped with aluminum oxide, gallium or indium.
  • the invention therefore aims to provide a white antistatic coating, suitable for application on spacecraft in particular.
  • the invention therefore relates to a composition
  • a "base” component comprising at least one doped zinc oxide-based pigment. with gallium oxide, a binder of the hydroxylated acrylic polymer type, a solvent of this binder.
  • composition may optionally further comprise a "hardener” component comprising at least one hardening agent; generally, the composition is then in the form of two separate components (kit).
  • a "hardener” component comprising at least one hardening agent
  • the level of hydroxyl functional groups in the acrylic or acrylate / polybutadiene polymer is between 1 and 10% by mass.
  • aromatic hydrocarbons toluene, xylene, styrene, naphtha, etc.
  • aliphatic hydrocarbons white spirit, gasoline, petroleum, etc.
  • ketones methyl ethyl ketone, methyl isobutyl ketone, diacetone.
  • esters ethyl acetate, methyl acetate, propyl acetate, ethylene glycol acetate, methylene glycol acetate, etc.
  • glycol ethers ethyl glycol, butyl glycol, methylene glycol, propylene glycol, etc.
  • aliphatic alkanes such as n-heptane and aromatic
  • esters such as n-heptane and aromatic
  • ketones such as terpene hydrocarbons (turpentine, etc.)
  • terpene hydrocarbons terpentine, etc.
  • Mention may be made more particularly of water, aliphatic and aromatic alkanes, esters, ketones and low molecular weight siloxanes, and in particular hexamethyldisiloxane, octamethyltrisiloxane and octamethylcyclotetrasiloxane.
  • the binder may be in emulsion or dispersion in water or soluble in said organic solvents.
  • the proportion of solvent may be up to 60% by weight of the "base”.
  • the pigment is preferably zinc oxide (ZnO) doped with Ga 2 O 3 , generally at 1-2% (weight) of Ga 2 O 3 .
  • the pigment according to the invention can be prepared by application or adaptation of methods known per se, such as by treatment in temperature and under a reducing atmosphere, and in particular according to the methods described in US 3,538,022 or US 5,312,614 .
  • the ZnO / Ga 2 O 3 pigment is generally used in dispersed or milled form.
  • the pigment may also comprise any other white pigment such as TiO 2 , ZnO, in proportions between 0 and 75% by weight.
  • Said curing agent is chosen from polyisocyanate type polymers, usually used for coatings. It is thus possible to mention, for example, polyisocyanates of the aliphatic polyisocyanate resin type, such as those of the DESMODUR® series, in particular DESMODUR N75, DESMODUR XP2487 / 1, etc., marketed by Bayer.
  • the "hardener” component may also include a solvent.
  • the "hardener” component may also comprise a solvent selected from water, hydrocarbons such as aliphatic and aromatic alkanes, esters, ketones, low molecular weight siloxanes, and mixtures thereof. More particularly, mention may be made of propylene glycol-based solvents, such as those of the Dowanol® series marketed by Dow, especially propylene glycol methyl ether acetate.
  • the "base” component and / or the “hardener” component may optionally further comprise a catalyst.
  • Said catalyst may be chosen from any catalyst used to promote cold or hot reactions, such as derivatives of tin or cobalt, such as tin dibutyldiacetate.
  • the catalyst can be included in a proportion of 0 to 10% by weight of the "base”. Generally, the catalyst is added in an amount such that the ratio (weight) catalyst: binder is less than 0.5%, preferably between 0.1 and 0.2%.
  • compositions according to the invention are such that the pigment: binder ratio is between 1 and 7 (weight).
  • said ratio pigment: binder by weight is between 1 and 4, even more preferably between 1 and 2.
  • the inventors have identified that the pigment: binder ratio makes it possible in particular to adjust the adhesion and electrical resistance properties of the composition.
  • the adhesion of the composition decreases.
  • the electrical resistance increases.
  • compositions of the invention may comprise in the "base” and / or the “hardener”, any desired adjuvants commonly used in coating formulations, provided, of course, that they do not excessively degrade the specifications. aforementioned techniques.
  • rheology agents and adjuvants can be used to improve the performance of adhesion, covering, drying or preservation in particular. It is thus possible to mention the AEROSIL® admixtures distributed by EVONIK Industries. The proportion of these agents can vary between 0.5 and 25% (weight) of the total composition.
  • the invention also relates to the process for preparing a composition according to the invention.
  • the method comprises the preparation of the "base” on the one hand by mixing its constituents and optionally the preparation of "hardener” on the other hand by mixing its constituents.
  • the type of equipment and tooling, as well as the shearing speed can be adapted by those skilled in the art according to usual practices to obtain a homogeneous dispersion conducive to obtaining a conductive film.
  • the present invention also relates to the coating that can thus be obtained by said method.
  • satellite paints must have low vacuum degassing (ESA Standard ECSS-Q-70-02A).
  • the coatings according to the invention may have a viscosity of between 10 and 30 sec AFNOR cut # 6 or 10 to 30 sec AFNOR cut # 4. They generally have a Newtonian or thixotropic rheological behavior.
  • the present invention also relates to substrates coated with a coating according to the invention.
  • Said substrates are generally any metal or dielectric support requiring such a coating, especially in the aeronautical, aerospace, military photovoltaic, electrical and chemical fields.
  • the coating of the invention can be applied to all kinds of substrates such as polyimides, composites of polyimides or epoxides reinforced with glass fibers, aramid fibers (Kevlar®), carbon fibers, glass, Kapton®, etc., or metals.
  • substrates such as polyimides, composites of polyimides or epoxides reinforced with glass fibers, aramid fibers (Kevlar®), carbon fibers, glass, Kapton®, etc., or metals.
  • the coatings of the invention may be applied in one or more layers to the substrate to be painted, and their thickness may vary from a few microns to a few millimeters depending on the intended applications. Generally, the thickness per layer is advantageously between 5 and 250 microns, with a surface electrical resistance of between 1 and 1000 M ⁇ / ⁇ .
  • the application of the coating layer of the invention to a substrate is carried out in the form of a paint film and can be carried out by manual or automatic mechanical spraying with a spray gun, a brush, a paintbrush, a stencil or by any other known technique.
  • adhesion primer for example adhesion or anti-corrosion primer
  • adhesion and anticorrosion primers MAPSIL® P255 red / clear, Alu-D, E 'and MAPSIL® SILICo, marketed by the company MAP may be applied.
  • adhesion primers MAPSIL® P255 clear, Alu-D, Kapt A and E 'especially marketed by the company MAP
  • adhesion primers can be advantageously applied.
  • the application of the coating can be advantageously carried out with simultaneous drying to evaporate the solvents.
  • Example 1 Paint thickness 35 ⁇ m 42 ⁇ m adherence 0/5 0/5 ⁇ p 0.28 0.29 In 0.89 0.89 R s 20 to 50 M ⁇ / ⁇ 20 to 50 M ⁇ / ⁇

Abstract

Composition comprises a base component comprising at least one pigment based on zinc oxide doped with gallium oxide, a binder of hydroxylated acrylic polymer, and a solvent of the binder. Independent claims are included for: (1) a preparation of the composition comprising preparation of the base on the one hand by mixing its constituents and optionally preparation of curing agent by mixing its constituents; (2) a process for preparing a coating comprising crosslinking of the base component of the composition; (3) the coating obtained by the method; and (4) a substrate coated with the coating.

Description

La présente invention concerne les revêtements conducteurs électriques pour la protection antistatique des substrats diélectriques ou métalliques, notamment d'engins spatiaux, et en particulier les lanceurs et satellites. Ces revêtements doivent répondre à plusieurs exigences : tout d'abord, il est primordial d'éviter l'accumulation de charge en surface. On recherche donc des peintures antistatiques pour éviter ces phénomènes dits de « flash over » (décharges électrostatiques en surface).The present invention relates to electrically conductive coatings for the antistatic protection of dielectric or metal substrates, especially spacecraft, and in particular launchers and satellites. These coatings must meet several requirements: first of all, it is essential to avoid the accumulation of charge on the surface. Antistatic paints are therefore sought to avoid these so-called "flash over" phenomena (surface electrostatic discharges).

Par ailleurs, ces revêtements doivent participer au contrôle thermique de l'engin. Il est donc important que la peinture soit blanche, pour permettre une réflexion totale des rayonnements solaires et éviter un échauffement de l'engin qui pourrait en résulter.In addition, these coatings must participate in the thermal control of the machine. It is therefore important that the paint is white, to allow total reflection of solar radiation and avoid a heating of the machine that could result.

Ainsi, ces peintures doivent répondre à des spécifications très strictes en termes d'absorption solaire (alpha), d'émissivité infrarouge (epsilon), de résistance électrique superficielle et d'adhérence.Thus, these paints must meet very strict specifications in terms of solar absorption (alpha), infrared emissivity (epsilon), surface electrical resistance and adhesion.

Dans la demande FR 2 568 577 est décrit un pigment d'oxyde d'étain dopé à l'oxyde d'antimoine ainsi que les peintures le contenant, permettant notamment l'élimination des charges électrostatiques. Néanmoins, ledit pigment, coloré, doit être mélangé avec un pigment blanc pour répondre aux exigences de faible absorption solaire. Par ailleurs, ce pigment est onéreux et ne répond plus aux normes environnementales européennes. Une peinture à base d'oxyde d'étain et d'oxyde d'antimoine est également décrite dans FR 2 668 491 . Néanmoins, là encore, l'ajout de dioxyde de titane est nécessaire pour rendre la peinture blanche.In the request FR 2,568,577 is described a tin oxide pigment doped with antimony oxide and the paint containing it, including the elimination of electrostatic charges. Nevertheless, said colored pigment must be mixed with a white pigment to meet the requirements of low solar absorption. Moreover, this pigment is expensive and no longer meets European environmental standards. A paint based on tin oxide and antimony oxide is also described in FR 2,668,491 . Nevertheless, again, the addition of titanium dioxide is necessary to make the paint white.

US 3,538,022 décrit une méthode de fabrication d'oxyde de zinc dopé par de l'oxyde d'aluminium, gallium ou indium. US 3,538,022 discloses a method of manufacturing zinc oxide doped with aluminum oxide, gallium or indium.

US 5,312,614 décrit également la production d'un pigment blanc à base d'oxyde de zinc, dopé par de l'oxyde de gallium, ledit pigment étant blanc et électriquement conducteur. Néanmoins, aucun de ces documents ne décrit une peinture contenant un tel pigment, notamment une peinture pour les applications spatiales répondant aux exigences techniques précitées. US 5,312,614 also discloses the production of a white pigment based on zinc oxide, doped with gallium oxide, said pigment being white and electrically conductive. Nevertheless, none of these documents describes a paint containing such a pigment, especially a paint for space applications meeting the aforementioned technical requirements.

L'invention a donc pour objet de fournir un revêtement blanc antistatique, convenant à l'application sur engins spatiaux notamment.The invention therefore aims to provide a white antistatic coating, suitable for application on spacecraft in particular.

Selon un premier objet, l'invention concerne donc une composition comprenant une composante « base » comprenant au moins un pigment à base d'oxyde de zinc dopé par de l'oxyde de gallium, un liant de type polymère acrylique hydroxylé, un solvant de ce liant.According to a first subject, the invention therefore relates to a composition comprising a "base" component comprising at least one doped zinc oxide-based pigment. with gallium oxide, a binder of the hydroxylated acrylic polymer type, a solvent of this binder.

Ladite composition peut éventuellement comprendre, en outre, une composante « durcisseur » comprenant au moins un agent durcisseur ; généralement, la composition se présente alors sous forme de deux composantes séparées (kit).Said composition may optionally further comprise a "hardener" component comprising at least one hardening agent; generally, the composition is then in the form of two separate components (kit).

Ledit liant peut être choisi notamment parmi :

  • les polymères acryliques hydroxylés, tel que par exemple ALBERDINGK® AC2597VP et/ou MACRYNAL® SM510N
  • les polymères acrylate/polybutadiène ou polyester hydroxylé habituellement utilisé pour les revêtements. On peut ainsi citer à titre illustratif les polyesters hydroxylés de type DESMOPHEN® commercialisés par Bayer, tel que DESMOPHEN 1100 et DESMOPHEN 651
Said binder may be chosen in particular from:
  • hydroxylated acrylic polymers, such as, for example, ALBERDINGK® AC2597VP and / or MACRYNAL® SM510N
  • the acrylate / polybutadiene or hydroxylated polyester polymers usually used for coatings. For example, mention may be made of hydroxylated polyesters of the DESMOPHEN® type marketed by Bayer, such as DESMOPHEN 1100 and DESMOPHEN 651.

Généralement, le taux de fonctions hydroxyles dans le polymère acrylique ou acrylate/polybutadiène est compris entre1 et 10 % massique.Generally, the level of hydroxyl functional groups in the acrylic or acrylate / polybutadiene polymer is between 1 and 10% by mass.

Comme solvant, on peut utiliser, à titre indicatif, des hydrocarbures aromatiques (toluène, xylène, styrène, naphta, etc.), des hydrocarbures aliphatiques (white spirit, essences, pétrole, etc.), des cétones (méthyléthylcétone, méthylisobutylcétone, diacétone alcool, etc.), des esters (acétate d'éthyle, acétate de méthyle, acétate de propyle, acétate d'étylèneglycol, acétate de méthylèneglycol, etc.), des éthers de glycol (éthylglycol, butylglycol, méthylèneglycol, propylèneglycol, etc.), des alcools (éthanol, propanol, méthanol, etc.), alcanes aliphatiques tel que le n-heptane et aromatiques, esters, cétones, siloxanes à faibles poids moléculaires notamment, des hydrocarbures terpéniques (essence de térébenthine, etc.), et de l'eau. On peut citer plus particulièrement l'eau, les alcanes aliphatiques et aromatiques, esters, cétones, siloxanes à faible poids moléculaire, et notamment l'hexaméthyldisiloxane, l'octaméthyltrisiloxane et l'octaméthylcyclotétrasiloxane.As a solvent, it is possible to use, as an indication, aromatic hydrocarbons (toluene, xylene, styrene, naphtha, etc.), aliphatic hydrocarbons (white spirit, gasoline, petroleum, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, diacetone). alcohol, etc.), esters (ethyl acetate, methyl acetate, propyl acetate, ethylene glycol acetate, methylene glycol acetate, etc.), glycol ethers (ethyl glycol, butyl glycol, methylene glycol, propylene glycol, etc. ), alcohols (ethanol, propanol, methanol, etc.), aliphatic alkanes such as n-heptane and aromatic, esters, ketones, low molecular weight siloxanes, especially terpene hydrocarbons (turpentine, etc.), and some water. Mention may be made more particularly of water, aliphatic and aromatic alkanes, esters, ketones and low molecular weight siloxanes, and in particular hexamethyldisiloxane, octamethyltrisiloxane and octamethylcyclotetrasiloxane.

Le liant peut être en émulsion ou dispersion dans l'eau ou soluble dans lesdits solvants organiques.The binder may be in emulsion or dispersion in water or soluble in said organic solvents.

La proportion de solvant peut aller jusqu'à 60 % en poids de la «base».The proportion of solvent may be up to 60% by weight of the "base".

Le pigment est préférentiellement de l'oxyde de zinc (ZnO) dopé par Ga2O3, généralement à 1-2% (poids) de Ga2O3. Le pigment selon l'invention peut être préparé par application ou adaptation de méthodes connues en soi, telles que par traitement en température et sous atmosphère réductrice, et notamment selon les méthodes décrites dans US 3,538,022 ou US 5,312,614 . Le pigment ZnO/ Ga2O3 est généralement utilisé sous forme dispersée ou broyée.The pigment is preferably zinc oxide (ZnO) doped with Ga 2 O 3 , generally at 1-2% (weight) of Ga 2 O 3 . The pigment according to the invention can be prepared by application or adaptation of methods known per se, such as by treatment in temperature and under a reducing atmosphere, and in particular according to the methods described in US 3,538,022 or US 5,312,614 . The ZnO / Ga 2 O 3 pigment is generally used in dispersed or milled form.

Le pigment peut également comprendre tout autre pigment blanc tel que TiO2, ZnO, dans des proportions entre 0 et 75% en poids.The pigment may also comprise any other white pigment such as TiO 2 , ZnO, in proportions between 0 and 75% by weight.

Ledit agent durcisseur est choisi parmi les polymères de type polyisocyanate, habituellement utilisés pour les revêtements. On peut ainsi citer à titre illustratif les polyisocyanates de type résine polyisocyanate aliphatique, tels que ceux de la série DESMODUR®, notamment DESMODUR N75, DESMODUR XP2487/1, etc., commercialisés par Bayer.Said curing agent is chosen from polyisocyanate type polymers, usually used for coatings. It is thus possible to mention, for example, polyisocyanates of the aliphatic polyisocyanate resin type, such as those of the DESMODUR® series, in particular DESMODUR N75, DESMODUR XP2487 / 1, etc., marketed by Bayer.

La composante « durcisseur » peut également comprendre un solvant.The "hardener" component may also include a solvent.

La composante «durcisseur» peut également comprendre un solvant choisi parmi l'eau, les hydrocarbures tels que les alcanes aliphatiques et aromatiques, esters, cétones, siloxanes à faible poids moléculaire, et leurs mélanges. On peut plus particulièrement citer les solvants à base de propylène glycol, tels que ceux de la série Dowanol ® commercialisés par Dow, notamment le propylèneglycolméthylétheracétate.The "hardener" component may also comprise a solvent selected from water, hydrocarbons such as aliphatic and aromatic alkanes, esters, ketones, low molecular weight siloxanes, and mixtures thereof. More particularly, mention may be made of propylene glycol-based solvents, such as those of the Dowanol® series marketed by Dow, especially propylene glycol methyl ether acetate.

La composante «base» et/ou la composante «durcisseur» peut éventuellement comprendre en outre un catalyseur. Ledit catalyseur peut être choisi parmi tout catalyseur utilisé pour favoriser les réactions à froid ou à chaud, tels que les dérivés de l'étain ou du cobalt notamment, tel que le dibutyldiacétate d'étain. Le catalyseur peut être compris à raison de 0 à 10 % en poids de la «base». Généralement, le catalyseur est ajouté en quantité telle que le rapport (poids) catalyseur : liant est inférieur à 0,5 %, préférentiellement compris entre 0,1 et 0,2%.The "base" component and / or the "hardener" component may optionally further comprise a catalyst. Said catalyst may be chosen from any catalyst used to promote cold or hot reactions, such as derivatives of tin or cobalt, such as tin dibutyldiacetate. The catalyst can be included in a proportion of 0 to 10% by weight of the "base". Generally, the catalyst is added in an amount such that the ratio (weight) catalyst: binder is less than 0.5%, preferably between 0.1 and 0.2%.

Généralement, les compositions selon l'invention sont telles que le rapport pigment : liant est compris entre 1 et 7 (poids). De préférence, ledit rapport pigment : liant en poids est compris entre 1 et 4, encore plus préférentiellement entre 1 et 2.Generally, the compositions according to the invention are such that the pigment: binder ratio is between 1 and 7 (weight). Preferably, said ratio pigment: binder by weight is between 1 and 4, even more preferably between 1 and 2.

Sans toutefois être liés par la théorie, les inventeurs ont identifié que le rapport pigment : liant permettait notamment d'ajuster les propriétés d'adhérence et de résistance électrique de la composition. Ainsi, lorsque ce rapport augmente, l'adhérence de la composition diminue. Inversement, lorsque ce rapport diminue, la résistance électrique augmente.Without however being bound by the theory, the inventors have identified that the pigment: binder ratio makes it possible in particular to adjust the adhesion and electrical resistance properties of the composition. Thus, as this ratio increases, the adhesion of the composition decreases. Conversely, when this ratio decreases, the electrical resistance increases.

Bien entendu, les compositions de l'invention peuvent comprendre dans la «base» et/ou le «durcisseur», tous adjuvants désirés communément employés dans les formulations de revêtements, à condition, bien sûr, qu'ils ne dégradent pas excessivement les spécifications techniques précitées. On peut ainsi citer par exemple les agents de rhéologie et adjuvants permettant d'améliorer les performances d'adhérence, couverture, séchage ou conservation notamment. On peut ainsi notamment citer les adjuvants de type AEROSIL® distribués par EVONIK Industries. La proportion de ces agents peut varier entre 0,5 et 25% (poids) de la composition totale.Of course, the compositions of the invention may comprise in the "base" and / or the "hardener", any desired adjuvants commonly used in coating formulations, provided, of course, that they do not excessively degrade the specifications. aforementioned techniques. For example, rheology agents and adjuvants can be used to improve the performance of adhesion, covering, drying or preservation in particular. It is thus possible to mention the AEROSIL® admixtures distributed by EVONIK Industries. The proportion of these agents can vary between 0.5 and 25% (weight) of the total composition.

Selon un autre objet, l'invention concerne également le procédé de préparation d'une composition selon l'invention.According to another object, the invention also relates to the process for preparing a composition according to the invention.

Le procédé comprend la préparation de la «base» d'une part par mélange de ses constituants et éventuellement la préparation du «durcisseur» d'autre part par mélange de ses constituants.The method comprises the preparation of the "base" on the one hand by mixing its constituents and optionally the preparation of "hardener" on the other hand by mixing its constituents.

Selon un autre objet, la présente invention concerne également le procédé de préparation d'un revêtement comprenant la réticulation de la composante «base»,

  • soit par mélange des composantes « base » et « durcisseur » lorsque la composition comprend une telle composante « durcisseur »; le mélange de la «base» et du «durcisseur» est habituellement réalisé sous agitation manuelle ou mécanique ;
  • soit le séchage physique de la composante «base», par action de la température, à température supérieure ou égale à 40°C.
According to another object, the present invention also relates to the process for preparing a coating comprising crosslinking of the "base" component,
  • either by mixing the "base" and "hardener" components when the composition comprises such a "hardener"component; the mixture of the "base" and the "hardener" is usually carried out with manual or mechanical stirring;
  • the physical drying of the "base" component, by the action of the temperature, at a temperature greater than or equal to 40 ° C.

Le type d'équipement et l'outillage, ainsi que la vitesse de cisaillement peuvent être adaptés par l'homme du métier selon des pratiques usuelles afin d'obtenir une dispersion homogène propice à l'obtention d'un film conducteur.The type of equipment and tooling, as well as the shearing speed can be adapted by those skilled in the art according to usual practices to obtain a homogeneous dispersion conducive to obtaining a conductive film.

Selon un autre objet, la présente invention concerne également le revêtement susceptible d'être ainsi obtenu par ledit procédé.According to another object, the present invention also relates to the coating that can thus be obtained by said method.

Le revêtement selon l'invention satisfait notamment aux normes réglementaires requises pour les engins spatiaux, à savoir :

  • facteur d'absorptivité solaire a inférieur ou égal à 0,3 ;
  • émissivité infra-rouge (ε) supérieure ou égale à 0,8 ;
  • résistance électrique superficielle comprise entre 1 et 1000 MΩ/□ selon la norme ASTMD 257-97 ou -98, -99 ou ASTM D257-07, telle que mesurée à la pression atmosphérique ou sous vide primaire (10-3 Torr) ;
  • adhérence de classe 0 ou 1 sur 5, de préférence 0 selon la norme NFEN ISO2409 (classement 30-038).
The coating according to the invention meets, in particular, the regulatory standards required for spacecraft, namely:
  • solar absorptivity factor a less than or equal to 0.3;
  • infrared emissivity (ε) greater than or equal to 0.8;
  • surface electrical resistance between 1 and 1000 MΩ / □ according to ASTMD 257-97 or -98, -99 or ASTM D257-07, as measured at atmospheric pressure or under primary vacuum (10 -3 Torr);
  • adhesion class 0 or 1 out of 5, preferably 0 according to NFEN ISO2409 (classification 30-038).

Les peintures pour satellites doivent, par ailleurs, présenter un faible dégazage sous vide (Norme ESA ECSS-Q-70-02A).In addition, satellite paints must have low vacuum degassing (ESA Standard ECSS-Q-70-02A).

Les revêtements selon l'invention peuvent présenter une viscosité comprise entre 10 et 30 s coupe AFNOR n °6 ou 10 à 30 s coupe AFNOR N °4. Ils ont généralement un comportement rhéologique de type newtonien ou thixotrope.The coatings according to the invention may have a viscosity of between 10 and 30 sec AFNOR cut # 6 or 10 to 30 sec AFNOR cut # 4. They generally have a Newtonian or thixotropic rheological behavior.

Selon un autre objet, la présente invention concerne également les substrats revêtus d'un revêtement selon l'invention. Lesdits substrats sont généralement tout support métallique ou diélectrique nécessitant un tel revêtement, notamment dans les domaines aéronautique, aérospatial, militaire photovoltaïque, électrique et chimique.According to another object, the present invention also relates to substrates coated with a coating according to the invention. Said substrates are generally any metal or dielectric support requiring such a coating, especially in the aeronautical, aerospace, military photovoltaic, electrical and chemical fields.

Le revêtement de l'invention peut être appliqué sur toutes sortes de substrats tels que des polyimides, des composites de polyimides ou d'époxydes renforcés de fibres de verre, de fibres d'aramide (Kevlar®), de fibres de carbone, verre, Kapton®, etc., ou des métaux.The coating of the invention can be applied to all kinds of substrates such as polyimides, composites of polyimides or epoxides reinforced with glass fibers, aramid fibers (Kevlar®), carbon fibers, glass, Kapton®, etc., or metals.

On peut ainsi citer les satellites, lanceurs ou tout élément de tels satellites ou lanceurs ainsi revêtus.We can cite the satellites, launchers or any element of such satellites or launchers thus coated.

Les revêtements de l'invention peuvent s'appliquer en une ou plusieurs couches sur le substrat à peindre, et leur épaisseur peut varier de quelques micromètres à quelques millimètres selon les applications envisagées. Généralement, l'épaisseur par couche est avantageusement comprise entre 5 et 250 µm, avec une résistance électrique superficielle comprise entre 1 et 1000 MΩ/□.The coatings of the invention may be applied in one or more layers to the substrate to be painted, and their thickness may vary from a few microns to a few millimeters depending on the intended applications. Generally, the thickness per layer is advantageously between 5 and 250 microns, with a surface electrical resistance of between 1 and 1000 MΩ / □.

L'application de la couche de revêtement de l'invention sur un substrat est réalisée sous forme de film de peinture et peut s'effectuer par pulvérisation mécanique manuelle ou automatique au pistolet à peinture, à la brosse, au pinceau, au pochoir ou par toute autre technique connue.The application of the coating layer of the invention to a substrate is carried out in the form of a paint film and can be carried out by manual or automatic mechanical spraying with a spray gun, a brush, a paintbrush, a stencil or by any other known technique.

Si désiré ou nécessaire, on peut appliquer une couche de primaire d'accrochage, ou toute autre couche primaire, par exemple primaire d'adhérence ou anti-corrosion, avant d'appliquer le revêtement de l'invention. Plus particulièrement dans le cas des substrats métalliques, les primaires d'adhérence et d'anticorrosion MAPSIL® P255 red/clear, Alu-D, E' et MAPSIL® SILICo, commercialisés par la société MAP pourront être appliqués. Dans le cas de supports diélectriques, des primaires d'adhérence (MAPSIL® P255 clear, Alu-D, Kapt A et E' notamment commercialisés par la société MAP) pourront être avantageusement appliqués.If desired or necessary, it is possible to apply a layer of primer, or any other primer, for example adhesion or anti-corrosion primer, before applying the coating of the invention. More particularly in the case of metal substrates, the adhesion and anticorrosion primers MAPSIL® P255 red / clear, Alu-D, E 'and MAPSIL® SILICo, marketed by the company MAP may be applied. In the case of dielectric supports, adhesion primers (MAPSIL® P255 clear, Alu-D, Kapt A and E 'especially marketed by the company MAP) can be advantageously applied.

L'application du revêtement peut être avantageusement réalisée avec un séchage simultané permettant d'évaporer les solvants.The application of the coating can be advantageously carried out with simultaneous drying to evaporate the solvents.

Les exemples suivants sont donnés à titre illustratif et non limitatif de la présente invention.The following examples are given by way of non-limiting illustration of the present invention.

Exemple 1 :Example 1

On mélange dans 21 g d'acrylate hydroxylé ALBERDINGK AC2597VP, 42 g de pigment ZnO/Ga2O3 », 28 g d'eau, 4 g d'adjuvants (AMP90). Par ailleurs, on prépare un mélange de 3,75 g de polyisocyanate DESMODUR XP2487/1 dans 1.25 g de solvants (DOWANOL® PMA).21 g of ALBERDINGK AC2597VP hydroxylated acrylate, 42 g of ZnO / Ga 2 O 3 pigment, 28 g of water and 4 g of adjuvants (AMP90) are mixed. Furthermore, a mixture of 3.75 g of polyisocyanate DESMODUR XP2487 / 1 in 1.25 g of solvents (DOWANOL® PMA) is prepared.

Puis, au moment de l'application, on mélange sous agitation mécanique les deux pré-mix.Then, at the time of application, the two premixes are mixed with mechanical stirring.

Exemple 2 :Example 2

On mélange dans 12 g d'acrylate hydroxylé MACRYNAL SM510N, 47 g de pigment ZnO/Ga2O3 », 23 g de DOWANOL PMA, 8 g d'adjuvants (AEROSIL® R 972). Par ailleurs, on prépare un mélange de 7,5 g de polyisocyanate DESMODUR N75 dans 2.5 g de solvants (DOWANOL® PMA).12 g of MACRYNAL SM510N hydroxyl acrylate, 47 g of ZnO / Ga 2 O 3 "pigment, 23 g of DOWANOL PMA and 8 g of adjuvants (AEROSIL® R 972) are mixed. Furthermore, a mixture of 7.5 g of DESMODUR N75 polyisocyanate in 2.5 g of solvents (DOWANOL® PMA) is prepared.

Exemple 3 :Example 3

- Les compostions selon les exemples 1 à 2 ci-dessus ont été testées pour leur épaisseur, adhérence, absorptivité, émissivité et résistance électrique superficielle. Les résultats sont résumés dans le tableau ci-dessous : Exemple 1 Exemple 2 Epaisseur peinture 35 µm 42 µm Adhérence 0/5 0/5 αp 0.28 0.29 En 0.89 0.89 Rs 20 à 50 MΩ/□ 20 à 50 MΩ/□ The compositions according to Examples 1 to 2 above were tested for their thickness, adhesion, absorptivity, emissivity and surface electrical resistance. The results are summarized in the table below: Example 1 Example 2 Paint thickness 35 μm 42 μm adherence 0/5 0/5 α p 0.28 0.29 In 0.89 0.89 R s 20 to 50 MΩ / □ 20 to 50 MΩ / □

Claims (15)

Composition comprenant une composante «base» comprenant au moins un pigment à base d'oxyde de zinc dopé par de l'oxyde de gallium, un liant de type polymère acrylique hydroxylé, un solvant de ce liant.Composition comprising a "base" component comprising at least one gallium oxide doped zinc oxide pigment, a hydroxylated acrylic polymer binder, a solvent of this binder. Composition selon la revendication 1 comprenant en outre une composante « durcisseur » comprenant au moins un agent durcisseur.The composition of claim 1 further comprising a "hardener" component comprising at least one curing agent. Composition selon la revendication 1 ou 2 telle que ledit liant est choisi parmi : - les polymères acryliques hydroxylés, - les polymères acrylate/polybutadiène hydroxylé ou polyester hydroxylé. Composition according to claim 1 or 2, such that said binder is chosen from: the hydroxylated acrylic polymers, hydroxylated acrylate / polybutadiene polymers or hydroxylated polyester. Composition selon la revendication 1, 2 ou 3 telle que le taux de fonctions hydroxyles dans le polymère acrylique ou acrylate/polybutadiène est compris entre 1 et 10% massique.A composition according to claim 1, 2 or 3 such that the level of hydroxyl functional groups in the acrylic or acrylate / polybutadiene polymer is between 1 and 10% by weight. Composition selon la revendication 1, 2 ou 3 telle que le pigment comprend l'oxyde de zinc (ZnO) dopé par Ga2O3.The composition of claim 1, 2 or 3 such that the pigment comprises zinc oxide (ZnO) doped with Ga 2 O 3 . Composition selon l'une quelconque des revendications précédentes telle que la composante «base» et/ou la composante « durcisseur » comprend en outre un catalyseur.A composition according to any of the preceding claims such that the "base" component and / or the "hardener" component further comprises a catalyst. Composition selon l'une quelconque des revendications précédentes telle que l'agent durcisseur est choisi parmi les polymères de type polyisocyanate.Composition according to any one of the preceding claims, such that the curing agent is chosen from polyisocyanate polymers. Composition selon l'une quelconque des revendications précédentes telle que la composante «durcisseur» comprend en outre un solvant.The composition of any preceding claim such that the "hardener" component further comprises a solvent. Composition selon l'une quelconque des revendications précédentes telle que le rapport pigment : liant est compris entre 1 et 7 (poids).Composition according to any one of the preceding claims, such that the pigment: binder ratio is between 1 and 7 (weight). Procédé de préparation d'une composition selon l'une quelconque des revendications 1 à 9 comprenant la préparation de la «base» d'une part par mélange de ses constituants et éventuellement la préparation du «durcisseur» d'autre part par mélange de ses constituants.Process for the preparation of a composition according to any one of Claims 1 to 9, comprising the preparation of the "base" on the one hand by mixing its constituents and possibly the preparation of the "hardener" on the other hand by mixing its constituents. Procédé de préparation d'un revêtement comprenant la réticulation de la composante «base» d'une composition selon l'une quelconque des revendications précédentes.A process for preparing a coating comprising crosslinking the "base" component of a composition according to any one of the preceding claims. Revêtement susceptible d'être obtenu par le procédé selon la revendication 11.Coating obtainable by the process according to claim 11. Revêtement selon la revendication 12 tel qu'il présente les caractéristiques suivantes : - facteur d'absorptivité solaire α inférieur ou égal à 0,3 ; - émissivité infra-rouge (ε) supérieure ou égale à 0,8 ; - résistance électrique superficielle comprise entre 1 et 1000 MΩ/□ selon la norme ASTMD 257-97 ou-98, -99, ou ASTM D257-07 telle que mesurée telle que mesurée à la pression atmosphérique ou sous vide primaire (10-3 Torr), - adhérence de classe 0 ou 1 sur 5 selon la norme NFEN ISO2409 (classement 30-038). The coating of claim 12 as having the following characteristics: - solar absorptivity factor α less than or equal to 0.3; - infrared emissivity (ε) greater than or equal to 0.8; - surface electrical resistance between 1 and 1000 MΩ / □ according to ASTMD 257-97 or -98, -99, or ASTM D257-07 as measured as measured at atmospheric pressure or under primary vacuum (10 -3 Torr) ) adhesion class 0 or 1 out of 5 according to standard NFEN ISO2409 (classification 30-038). Substrat revêtu d'un revêtement selon la revendication 12 ou 13.Coated substrate according to claim 12 or 13. Substrat selon la revendication 14 choisi parmi les satellites, lanceurs ou tout élément de tels satellites ou lanceurs.Substrate according to claim 14 selected from satellites, launchers or any element of such satellites or launchers.
EP11305398A 2010-04-08 2011-04-06 Weiße Antistatikbeschichtung auf der Basis von hydroxyliertem Acryl Active EP2374716B1 (en)

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CN112062921A (en) * 2020-08-24 2020-12-11 无锡市耀得信化工产品有限公司 Zinc salt-containing acrylic polyurethane resin and preparation method and application thereof
CN112062922B (en) * 2020-08-24 2022-04-29 无锡市耀得信化工产品有限公司 Polyurea modified organic zinc salt-containing acrylic resin and preparation method and application thereof

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US20110251327A1 (en) 2011-10-13
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ES2396690T3 (en) 2013-02-25

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